Development of New Reactions for Synthesis of Cyclopentanoids and their Application

环戊烷合成新反应的进展及其应用

• 批准号: 13650913
• 负责人: KOBAYASHI Yuichi
• 金额: $ 2.24万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650913/
• 关键词: cyclopentene-1,3-diol; Grrignard Reagent; Organocopper; S_N2; anti S_N2'; 12-oxo-PDA; OPC:8-0; Δ^<12>-PGJ_2; 4-シクロペンテン-1,3-ジオール; Grignard試薬; 銅触媒; シクロペンタノイド; 12-oxo-PDAの合成; OPC-8:0; エピジャスモン酸; PPARγアゴニスト; シクロペンタノイドム; Δ^<13>-PGJ_2; シンクロペンテン

4-Cyclopentene-1,3-diol monoacetate (1) is an attractive compound for synthesis of cyclopentanoids. However, the use along this line had been limited due to lack of efficient reactions for installation of carbon nucleophiles onto the ring. Herein, we have developed new reactions based on RMgX and Cu(I) for S_N2 and anti S_N2' reactions, thus producing 4-substituted 2-cyclopenten-1-ols (1,4-isomers) or 2-substituted 3-cyclopenten-1-ols (1,2-isomers) depending on the ratio of RMgZ/Cu(I) and solvent used. In addition, we developed reagents and conditions for attaching second carbon nucleophiles to the 1,4-isomers produced above. We applied these reactions to synthesis of 12-oxo-PDA, OPC-8:0, OPC-8:0, and Δ^<12>-PGJ_2.

4-胞烯烯-1,3-二醇单乙酸酯（1）是用于合成环戊糖苷的有吸引力的化合物。然而，由于缺乏有效的反应来安装碳核pholipheles，沿着这条线的使用受到限制。 Herein, we have developed new reactions based on RMgX and Cu(I) for S_N2 and anti S_N2' reactions, thus producing 4-substituted 2-cyclopenten-1-ols (1,4-isomers) or 2-substituted 3-cyclopenten-1-ols (1,2-isomers) depending on the ratio of RMgZ/Cu(I) and solvent used.此外，我们开发了将第二个碳核硫杆菌连接到上面产生的1,4异构体的试剂和条件。我们将这些反应应用于12-oxo-PDA，OPC-8：0，OPC-8：0和δ^<12> -pgj_2的合成。

项目成果

T.Ainai: "Efficient Total Synthesis of 12-Oxo-PDA and OPC-8:0"J.Org.Chem.. 68. 7825-7832 (2003)

T.Ainai：“12-Oxo-PDA 和 OPC-8:0 的高效全合成”J.Org.Chem.. 68. 7825-7832 (2003)

Y.Kobayashi: "Installation of Carbon Nucleophiles onto Monoacetate of 4-Cyclopentene-1,3-diol and Synthesis of Cyclopentanoids"Current Org.Chem.. 7. 133-147 (2003)

Y.Kobayashi：“将碳亲核试剂安装到 4-环戊烯-1,3-二醇单乙酸酯上并合成环戊烷”Current Org.Chem.. 7. 133-147 (2003)

H.P.Acharya: "Total Synthesis of D^<12>-PGJ_2, 15-deoxy-D^<12,14>-PGJ_2, and Related Compounds"Tetrahedron Lett.. 45. 1199-1202 (2004)

H.P.Acharya：“D^<12>-PGJ_2、15-脱氧-D^<12,14>-PGJ_2 和相关化合物的全合成”Tetrahedron Lett.. 45. 1199-1202 (2004)

M.Matsuumi: "Introduction of a Hydroxylmethyl Group Onto the Ring of 4-Cyclopentene-1,3-diol Monoacetate"Synlett. 1508-1510 (2002)

M.Matsuumi：“在 4-环戊烯-1,3-二醇单乙酸酯环上引入羟甲基”Synlett。

Y.Kobayashi: "A New Method for Installation of Aryl and Alkenyl Groups onto a Cyclopentene Ring and and Synthesis of Prostaglandins"J.Org.Chem.. 67. 7110-7123 (2002)

Y.Kobayashi：“在环戊烯环上安装芳基和烯基以及合成前列腺素的新方法”J.Org.Chem.. 67. 7110-7123 (2002)